Development and testing of a Frisch-Grid Ionization Chamber for the measurement of low activity of alpha-particle emitters

Journal of Radioanalytical and Nuclear Chemistry - A Frisch-grid Ionization Chamber (FGIC) for the measurement of low activity of alpha-particle emitters has been built. The design and performance...     

Higher integrability for nonlinear elliptic equations with variable growth and discontinuous coefficients

In this paper, based on the theory of variable exponent spaces, we study the higher integrability for a class of nonlinear elliptic equations with variable growth and discontinuous coefficients. Under suitable assumptions, we obtain a local gradient estimate in Orlicz space for weak solution.     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

Six mono/double‐layered 2D and three 3D coordination polymers were synthesized by a self‐assembly reaction of Zn (II) salts, organic dicarboxylic acids and L1/L2 ligands. These polymeric formulas are named as [Zn(L1)(C₄H₂O₄)_0.5 (H₂O)]_n·0.5n(C₄H₂O₄)·2nH₂O ( 1 ), [Zn₂(L2)(C₄H₂O₄)₂]_n·2nH₂O ( 2 ), [Zn(L1)(m‐BDC)]_n ( 3 ), [Zn₂(L2)(m‐BDC)₂]_n·2nH₂O ( 4 ), [Zn₃(L1)₂(p‐BDC)₃(H₂O)₄]_n·2nH₂O ( 5 ), [Zn₂(OH)(L2) (p‐BDC)_1.5]_n ( 6 ), [Zn₂(L1)(p‐BDC)₂]_n·5nH₂O ( 7 ), [Zn₂(L2)(p‐BDC)₂]_n·3nH₂O ( 8 ) and [Zn₂(L1)(C₄H₄O₄)_1.5(H₂O)]_n·n(ClO₄)·nH₂O ( 9 ) [L1 = N,N′‐bis (pyridin‐4‐ylmethyl)propane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethyl)propane‐1,2‐ diamine, m‐BDC^2? = m‐benzene dicarboxylate, p‐BDC^2? = p‐benzene dicarboxylate]. Meanwhile, these polymers have been characterized by elemental analysis, infrared, thermogravimetry (TG), photoluminescence, powder and single‐crystal X‐ray diffraction. Polymers 1–6 present mono‐ and double (4,4)‐layer motifs accomplished by L1/L2 ligands with diverse conformations and organic dicarboxylates, and the layer thickness locates in the range of 5.8–15.0 Å. In three 3D polymers, the L1 and L2 molecules adopt the same cis‐conformations and join adjacent Zn (II) cations together with p‐BDC^2? or succinate, giving rise to different binodal (4,4)‐c nets with (4.5².8³)(4.5³.7²) ( 7 ), pts ( 8 ) topology and twofold interpenetrated binodal (5,5)‐c nets with (3².4⁴.5².6²)(3.4³.5².6⁴) ( 9 ). Therefore, the diverse conformations of the two bis (pyridyl)‐propane‐1,2‐diamines and the feature of different organic dicarboxylate can effectively influence the architectures of these polymers. Powder X‐ray diffraction patterns demonstrate that these bulk solid polymers are pure phase. TG analyses indicate that these polymers have certain thermal stability. Luminescent investigation reveals that the emission maximum of these polymers varies from 402 to 449 nm in the solid state at room temperature. Moreover, 1 , 3 and 5–8 show average luminescence lifetimes from 8.81 to 16.30 ns.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).     

Octahedral Chiral‐at‐Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions

Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid.     

Triphenylphosphine-m-sulfonate/carbon tetrabromide as an easily recoverable catalyst system for the efficient synthesis of xanthene and xanthenone derivatives under solvent-free conditions

A solid complex,readily prepared from commercially available sodium triphenylphosphine-m-sulfonate（TPPMS） and carbon tetrabromide,can be used as an easily recoverable and reusable catalyst system for one-pot condensation of 2-naphthol with aldehydes to construct 14-aryl（alkyl）-14H-dibenzo[a j]-xanthene derivatives and one-pot condensation of 2-naphthol with aldehydes and cyclic 1 3-dicarbonyl compounds to construct 12-aryl（alkyl）-8 9 10 12-tetrahydrobenzo[a]xanthen-11-one derivatives.     

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene-hydride of Cp2M(L)H [Cp = η5-C5H5; M = Nb,V; L = CO,P (OMe)3]: A DFT study

The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp₂M(L)H [Cp = η⁵-C₅H₅; M = Nb, V; L = CO, P (OMe)₃] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG^#). Then the Z-pro converts to E-pro , while for L = P (OMe)₃, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp₂M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp₂V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp₂M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.